CN104409564A - N-type nanometer black silicon manufacturing method and solar cell manufacturing method - Google Patents
N-type nanometer black silicon manufacturing method and solar cell manufacturing method Download PDFInfo
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- CN104409564A CN104409564A CN201410605032.4A CN201410605032A CN104409564A CN 104409564 A CN104409564 A CN 104409564A CN 201410605032 A CN201410605032 A CN 201410605032A CN 104409564 A CN104409564 A CN 104409564A
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- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 93
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 239000004332 silver Substances 0.000 claims abstract description 29
- 230000007797 corrosion Effects 0.000 claims abstract description 28
- 238000005260 corrosion Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 85
- 239000010703 silicon Substances 0.000 claims description 85
- 238000005530 etching Methods 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000012937 correction Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002310 reflectometry Methods 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 5
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- 230000006798 recombination Effects 0.000 description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses an N-type nanometer black silicon manufacturing method and a solar cell manufacturing method. The N-type nanometer black silicon manufacturing method comprises steps that: (1), silicon chips after cleaning react in mixed solution of KOH and isopropanol for 0.5-2 hours, and the reaction temperature is 60-100 DEG C; and (2), the N-type silicon chips treated in the step (1) are put in a silver nanometer particle solution for 20-30 minutes in a standing mode, after drying, corrosion treatment on the treated N-type silicon chips is carried out to acquire the N-type nanometer black silicon. For manufacturing a solar cell, an N+ layer, a silicon nitride layer and an electrode layer are sequentially formed at the front surface of the manufactured N-type nanometer black silicon, after sintering, the N-type nanometer black silicon solar cell is manufactured. The manufactured N-type nanometer black silicon solar cell has properties of low reflectivity and high carrier service life and has the conversion efficiency 2.2% higher than that of a cell manufactured through a routine method.
Description
Technical field
The present invention relates to field of photovoltaic technology, be specifically related to a kind of preparation method of N-type nano black silicon and the preparation method of solar cell.
Background technology
Optical loss is the principal element hindering solar battery efficiency to improve, and reducing solar cell optical loss is improve the important and approach effectively of of battery efficiency.Current crystalline silicon mainly adopts at silicon chip surface preparation " pyramid " texture anti-reflection structure to reduce reflectivity, but its at visible light wave range average reflectance more than 10%, the reflection loss of light is still larger, governs the further raising of solar battery efficiency.
The black silicon structure of nanoporous effectively can reduce the anti-reflection structure of reflectivity.It can adopt electrochemical process and the preparation of metal auxiliary catalysis.Metal auxiliary catalysis, because preparation technology is relatively simple, all possesses good anti-reflective effect to monocrystalline, polycrystalline, has potential industrial application value, so receive increasing concern.
The black silicon structure of the nanoporous utilizing metal auxiliary catalysis to prepare on pyramid texture can obtain low-down reflectivity, but because loose structure significantly adds silicon chip specific area, cause Carrier recombination very serious, thus cause the short circuit current of battery lower, make battery efficiency cannot reach commercial solar cell efficiency high like that.People (the Jihun Oh* such as photovoltaic center, National Renewable Energy laboratory Jihun Oh, Hao-Chih Yuan and Howard M.Branz.An 18.2%-efficientblack-silicon solar cell achieved through control of carrier recombination innanostructures.Nature Nano technology, 2012, 7:743-748) by using tetramethylammonium hydroxide (tetramethy lammonium hydroxide, TMAH) etching correction is carried out to the nanometer light trapping structure prepared, effectively reduce specific area and the hole density of silicon chip surface, thus prepared high efficiency black silion cell.But TMAH cost is higher, causes obstacle for commercial application.Thus the target that a kind of etching agent simultaneously possessing good etching effect with low cost becomes everybody exploration is sought.
In addition, the black silicon structure of current most of nanoporous is all prepare on P-type silicon sheet, and compared with P-type silicon sheet, the minority carrier lifetime of the N-type silicon chip of same resistivity is higher than P-type silicon sheet, this mainly has more boron-oxygen relevant to the effect serving complex centre with in boron doped P-type silicon sheet, and the tolerance of N-type silicon chip to metallic pollution is higher than P-type silicon sheet, this point will have advantage more for utilizing silver nano-grain catalyzed corrosion to prepare nano black silicon structure.So compared with P-type silicon sheet, the silicon chip that N-type silicon chip prepares nano-porous structure will have higher minority carrier life time, this will be for improving the short circuit current of battery by helpful.
Summary of the invention
The object of the invention is by preparing nanometer light trapping structure on N-type czochralski silicon sheet surface, reduce silicon chip surface specific area by alkaline etching simultaneously, reduce Carrier recombination, increase minority carrier life time, thus effectively improve battery efficiency, finally silicon chip is prepared high efficiency N+NP back junction solar battery according to existing P type black silicon solar cell production technology.
The preparation method of black silicon of the present invention, comprises the following steps:
(1) make the reaction 0.5 ~ 2h in the mixed solution of KOH and isopropyl alcohol of the silicon chip after cleaning, reaction temperature is 60 ~ 100 DEG C, and silicon chip surface forms pyramid structure of uniform size.
Cleaning method is as follows: make N-type silicon chip be placed in KOH solution and clean, and removes silicon chip surface damage;
Scavenging period is relevant with the concentration of KOH solution, is generally 10 ~ 20min.Preferably, the concentration of described KOH solution is 15 ~ 30mt% (mt% represents molar percentage), removes silicon chip surface damage.Enter optimally, the concentration of described KOH solution is 20mt%.
Preferably, in the mixed solution of KOH and isopropyl alcohol, the mass concentration of KOH is 3%, and the volumetric concentration of isopropyl alcohol is 7%.
Further preferably, the reaction temperature of described reaction is 80 DEG C, and the corresponding reaction time is 60min.
(2) N-type silicon chip after step (1) process is placed in silver nano-grain solution and leaves standstill 20min ~ 30min, carry out corrosion treatment and namely obtain N-type nano black silicon after drying.
Silicon chip can form layer of oxide layer in atmosphere; the surface of silica is hydrophilic; so the silver nano-grain in solution can form good contact with silicon chip surface, leave standstill silver nano-grain in process and can be deposited on silicon chip surface, using the catalyst as subsequent reactions.
As preferably, in silver nano-grain solution of the present invention, the size (particle diameter) of silver nano-grain is 50 ~ 100nm, and even size distribution.
The present invention prepares the aqueous solution that silver nano-grain solution is actually silver nano-grain by the following method, and concentration can need setting according to practical application, is generally 0.02 ~ 0.1mol/L, as being preferably 0.05mol/L.Adopt and prepare silver nano-grain with the following method, and then the silver nano-grain obtained is configured to the silver nano-grain solution of desired concn.Wherein, the preparation method of silver nano-grain is as follows:
At 35 DEG C, by 37vol%CH
2o joins 0.1mol/L AgNO
3in solution, with mass concentration be polyvinylpyrrolidone (PVP) K-30 of 0.75% ~ 3% as surfactant, then add 28vol% ammoniacal liquor and impel reaction, be uniformly mixed reaction 30min, then add alcohol centrifugal four times, obtain the silver nano-grain of about 50 ~ 100nm.
Silver nano-grain size can control by regulating the amount of polyvinylpyrrolidone PVP K-30, makes Argent grain size Control within the scope of 50 ~ 100nm.Temperature controls at 35 DEG C, because the reducing power of formaldehyde and temperature is in close relations, the higher reaction of temperature is faster.Growth temperature also may affect the reunion of Ag particle.In reunion growth, the speed of growth of Argent grain is accelerated when temperature raises.In the later stage in interstage, the surface potential of Ag particle reduces along with the rising of temperature.At low temperatures, due to electrostatic repulsion forces, reunion speed is very low.Along with the rising of temperature, surface potential reduces, and causes weak repulsive force and the high speed of growth.
The N-type silicon chip forming pyramid structure in described step (2) carries out corrosion treatment.As preferably, corrosion process is specific as follows:
Make the N-type silicon chip after step (2) process be placed in corrosive liquid and carry out corrosion reaction under shading environment, described etchant solution is HF, H
2o
2with the mixed liquor of deionized water.
As preferably, HF, H in described corrosive liquid
2o
2be 1:(4 ~ 6 with the volume ratio of deionized water): (8 ~ 12).Further, HF, H in described corrosive liquid
2o
2be 1:5:10 with the volume ratio of deionized water.
Corrosion reaction at room temperature can be carried out.Preferably, the reaction duration of corrosion reaction is 3min ~ 6min.
Because H
2o
2see that light easily decomposes, therefore reaction need be carried out in light-shielding container.Corrosive liquid can be held by adopting shading reaction vessel in the present invention, carrying out under shading environment to make corrosion reaction.
Make silicon chip surface can obtain uniform nanoporous shape structure by corrosion, this structure has very strong light trapping effect, namely as light trapping structure.
Silicon chip after usual shape corrosion has become black silicon, and for strengthening sunken luminous effect further, further preferably, the N-type silicon chip after corrosion removal carries out etching correction (be actually the light trapping structure corroding formation most and proceed etching correction).
Through over etching correction, the corrosion depth in nanoporous light trapping structure can shoal, and aperture increases, and the specific area of silicon chip surface reduces, and surface recombination also reduces.
As preferably, the N-type silicon chip after directly making corrosion treatment when etching is revised is revised in solution in etching and is reacted, and described etching correction solution is alkaline solution, as TMAH, NaOH etc., can be also acid solution, as H
2o
2and HNO
3mixed liquor.
Consider from cost and effect, as preferably, it be concentration is 1 ~ 5wt% (wt% represents mass percent) that described etching revises solution, and NaOH solution, reaction duration is 2 ~ 4min.Optimally, the concentration of the NaOH solution adopted during etching is 2wt%, and reaction duration is 3min.
The remnants of silver nano-grain are had through the silicon chip surface of corrosion reaction; these silver nano-grains can affect subsequent applications effect; during as the black silicon structure obtained is applied to solar cell; can diffuse in silicon chip in expansion phosphorus process when preparing solar cell and form Carrier recombination center; reduce minority carrier lifetime, and then affect battery performance.
Alkali concn is too high reacts violent with time long all can causing, and easily all etched away by the nanometer light trapping structure (i.e. light trapping structure) prepared, the too low then reflection of concentration is slow, needs the longer reaction time.
After alkaline etching, silicon chip surface has sodium ion to be existed, and needs to remove with hydrochloric acid.Sodium ion is remained by the N-type silicon chip after having etched.Therefore, further the revised N-type silicon chip of etching is placed in the hydrochloric acid reaction 2 ~ 5min of 10vol%, then cleans and dry up and namely obtain final nano black silicon.Usual employing washed with de-ionized water, adopts nitrogen to dry up.
As preferably, described step (2) also comprises the N-type silicon chip after to corrosion and goes residual treatment with except removing residual silver nano-grain.In the present invention, the N-type silicon chip after corrosion is put into 65wt%HNO
31min is placed to remove remaining silver nano-grain in solution.
Present invention also offers a kind of preparation method of N-type black silicon solar cell, first N-type nano black silicon is prepared, then N+ layer, silicon nitride layer and electrode layer is formed successively at the front surface of the N-type nano black silicon prepared, finally namely obtain N-type black silicon solar cell carrying out sintering, described N-type nano black silicon is prepared by above-mentioned steps (1) ~ (3).
Carry out gaseous state diffusion according to existing P type manufacture of solar cells technique in the present invention and expand phosphorus to form N+ layer at front surface, silicon nitride layer is prepared by PECVD method.Electrode layer is prepared by silk screen print method, and this adopts full aluminium to carry on the back silk screen print method.
One aspect of the present invention rests on silicon chip surface by the silver nano-grain that size is controlled, the low-down nanometer light trapping structure of reflectivity is prepared by silver-colored catalyzed corrosion under room temperature, then surface recombination is reduced by alkaline etching having on antiradar reflectivity light trapping structure basis, increase minority carrier lifetime, thus effectively improve short circuit current and the open circuit voltage of battery.Although reflectivity can rise to some extent in this process, but still lower than 5.5%, compared to the reflectivity of the anti-reflection structure more than 10% of existing industry, be decline by a relatively large margin, and battery efficiency to improve 2.2% compared to the battery without alkaline etching.On the other hand, the present invention adopts the N-type silicon chip higher to metal impurities tolerance, because the minority carrier lifetime of the N-type silicon chip of same resistivity is higher than P-type silicon sheet, thus N-type silicon chip is more conducive to the impact that reduction nano black silicon structure surface recombination is seriously brought.
Do not make specified otherwise in the present invention, described N-type silicon chip is N-type czochralski silicon sheet, and N-type silicon chip size is according to reality, and resistivity is 1 ~ 10 Ω cm.
Compared with prior art, this invention has following advantage:
Nanometer light trapping structure is prepared in the catalysis on N-type czochralski silicon sheet of a silver nano-grain that () the present invention adopts size controlled, and this structure prepares on silicon chip pyramid structure basis, and reflectivity can drop to less than 2.4%.The sodium hydroxide solution of low concentration is adopted to etch this kind of structure afterwards, by reducing the corrosion depth of light trapping structure and expanding aperture, thus reduce silicon chip surface specific area, surface recombination is reduced, minority carrier increases, although etch revised silicon chip reflectivity also correspondingly to rise, but still lower than 5.5%.The conversion efficiency of this kind of battery is compared conventional method and is wanted high by 2.2%;
B () manufacture craft processing procedure of the present invention is simple, quick, the preparation method of preparation technology and P-type silicon solar cell is compatible, do not need to add any main equipment, the cost of raw material related to is lower, and can realize with existing industrial manufacture process compatible well, after process, the surface reflectivity of silicon chip is low, and minority carrier life time is higher, and battery efficiency can reach 17.8%.
Accompanying drawing explanation
Fig. 1 is the SEM figure on the N-type silicon chip surface of corroding 0min in embodiment 1;
Fig. 2 is the SEM figure on the N-type silicon chip surface of corroding 4min in embodiment 1;
Fig. 3 be corrode 3 in embodiment 1,4,5,6min time the reflectance map of silicon chip;
Fig. 4 is the reflectance map corroding the N-type silicon chip table that 0min and 4min and embodiment 2 obtain in embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The preparation method of the N-type nano black silicon of the present embodiment comprises the steps:
(1) by soluble in water for 1.5g polyvinylpyrrolidone (PVP K-30), form 50g base fluid, in base fluid, the mass concentration of formaldehyde is 0.74%, in base fluid, the mass concentration of polyvinylpyrrolidone is 3%, in base fluid, drip silver nitrate aqueous solution mass concentration is 1.7%, quick injection ammoniacal liquor (mass fraction is the solution 0.6ml of 28%), 30min is reacted at 35 DEG C, obtain the solution of silver nano-grain, then alcohol is added centrifugal four times, obtain silver nano-grain, silver nano-grain is spherical, silver nano-grain size (particle diameter) is 50nm ~ 100nm.
(2) N-type silicon chip (the primary silicon chip of N-type pulling of crystals) being of a size of 156mm × 156mm is dropped in 20mt%KOH solution, under 80 DEG C of conditions, react 2min, remove damaged layer on surface of silicon slice.
(3) silicon chip after cleaning is put into the mixed solution of KOH and isopropyl alcohol, wherein the mass concentration of KOH is 3%, and the volumetric concentration of isopropyl alcohol is 7%, reacts 60min, form pyramid structure of uniform size at silicon chip surface under 80 DEG C of conditions.
(4) silicon chip with pyramid structure of step (3) is put into silver nano-grain solution left standstill 20min, then dry, the surface texture of the N-type silicon chip obtained is as Fig. 1.
The minority carrier life time being obtained now N-type silicon chip by minority carrier lifetime tester test is 10.18 μ s.Carry out reflectance test further, the reflectivity obtained is as shown in curve a in Fig. 4, and reflectivity is 13.4%.
(5) silicon chip of step (4) is put into the shading reaction vessel that corrosive liquid is housed, at room temperature reacts 3 respectively, 4,5,6min, corrosive liquid is HF, H
2o
2with the mixed liquor of deionized water, solution ratio is 1:5:10 (volume ratio), forms nanometer light trapping structure, namely obtain the monocrystalline silicon solar battery suede of low surface reflectivity, namely N-type nano black silicon on pyramid surface.
Fig. 2 is scanning electron microscopy (SEM) figure of silicon chip surface after corrosion 4min.From Fig. 2 comparison diagram 1, after catalyzed corrosion 4min, loose structure uniform fold, on N-type silicon chip surface, forms nanometer light trapping structure.
Fig. 3 is the reflectivity collection of illustrative plates of the silicon chip under the different catalyzed corrosion time, and the average reflectance as seen in 300 ~ 1100nm wave-length coverage is reduced to less than 2.4%.Wherein corrode 3,4,5, reflectivity that 6min is corresponding is respectively 2.2%, 1.9%, 2.0% and 2.3%.
The minority carrier life time 2.73 μ s corroding the N-type nano black silicon that 4min obtains is obtained through minority carrier lifetime tester test.
(6) silicon chip of step (5) is put into 65wt%HNO3 solution and place 1min, remove remaining silver nano-grain.
Also carry out gaseous state diffusion according to existing P type manufacture of solar cells technique in the present embodiment and expand phosphorus at front surface formation N+ layer, PECVD plating silicon nitride, silk screen printing and sintering.But silk screen printing will adopt full aluminium to carry on the back printing.
The solar cell obtained in the present embodiment is nano black silicon N+NP solar cell.Under AM 1.5 light intensity, utilize every electric property of cell piece efficiency separator test battery, test result is as shown in table 1.Wherein, Voc is open circuit voltage, and Isc is short circuit current, and FF is fill factor, curve factor, and η is conversion efficiency, and τ is the minority carrier life time of silicon chip after making herbs into wool.
For ease of contrast, in table 1, also list the electric property of existing N+NP solar cell (i.e. prior art) under AM 1.5 light intensity and minority carrier life time.Existing N+NP solar cell refers to that surface is not prepared nanometer light trapping structure and only has the N+NP solar cell of pyramid structure (being the N-type silicon chip in corrosion 0min).
Table 1
Embodiment 2
Identical with embodiment 1, difference is that in step (5), etch period is 4min, and also carries out etching correction by following process to the N-type silicon chip after step (5) process between step (6) and step (7):
N-type silicon chip after step (6) being processed is put into 2wt%NaOH solution and is reacted 3min, to carry out etching correction to the nanometer light trapping structure obtained in step (5).And then hydrochloric acid 2min silicon chip being put into 10vol% is to remove sodium ion, then use washed with de-ionized water silicon chip, then dry up with nitrogen.
The nano black silicon N+NP solar cell prepared by the present embodiment 2 utilizes every electric property of cell piece efficiency separator test battery under AM 1.5 light intensity, and result is as shown in table 1.
The life-span of few son of the N-type nano black silicon that the present embodiment prepares is 5.19 μ s, and corresponding reflectivity is as shown in curve c in Fig. 4, and reflectivity is 5.4%.For ease of comparing, in Fig. 4, give the reflectance curve of the N-type silicon chip of corroding 4min in embodiment 1, as shown in curve b.
Discovery is compared to the test parameter of the various embodiments described above, although etch revised silicon chip reflectivity also correspondingly to rise, but still lower than 5.5%, and the conversion efficiency of solar cell is higher by 2.2% than the conversion efficiency of only corroding solar cell corresponding to 4min in embodiment after over etching correction.
Above-described embodiment has been described in detail technical scheme of the present invention and beneficial effect; be understood that and the foregoing is only most preferred embodiment of the present invention; be not limited to the present invention; all make in spirit of the present invention any amendment, supplement and equivalent to replace, all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for N-type nano black silicon, is characterized in that, comprises the following steps:
(1) make the reaction 0.5 ~ 2h in the mixed solution of KOH and isopropyl alcohol of the N-type silicon chip after cleaning, reaction temperature is 60 ~ 100 DEG C;
(2) N-type silicon chip after step (1) process is placed in silver nano-grain solution and leaves standstill 20min ~ 30min, carry out corrosion treatment and namely obtain N-type nano black silicon after drying.
2. the preparation method of N-type nano black silicon as claimed in claim 1, is characterized in that, also comprises the N-type silicon chip after to corrosion treatment and carry out etching correction in described step (2).
3. the preparation method of N-type nano black silicon as claimed in claim 2, is characterized in that, the N-type silicon chip after making corrosion treatment when etching is revised is revised in solution in etching and reacted.
4. the preparation method of N-type nano black silicon as claimed in claim 3, is characterized in that, the NaOH solution of described etching correction solution to be concentration be 1 ~ 5wt%.
5. the preparation method of N-type nano black silicon as claimed in claim 4, is characterized in that, reaction duration when etching is revised is 2 ~ 4min.
6. as the preparation method of the N-type nano black silicon in claim 2 ~ 5 as described in any one claim, it is characterized in that, etching also comprises the N-type silicon chip after to corrosion treatment and goes residual treatment with the silver nano-grain remained except removal before revising.
7. the preparation method of N-type nano black silicon as claimed in claim 6, it is characterized in that, the N-type silicon chip after making oven dry in described step (2) reacts 3min ~ 6min to complete corrosion treatment in corrosive liquid, and described corrosive liquid is HF, H
2o
2with the mixed liquor of deionized water.
8. the preparation method of N-type nano black silicon as claimed in claim 7, is characterized in that, HF, H in described corrosive liquid
2o
2be 1:(4 ~ 6 with the volume ratio of deionized water): (8 ~ 12).
9. the preparation method of a solar cell, it is characterized in that, employing such as the preparation method in claim 1 ~ 7 as described in any one claim prepares N-type nano black silicon, then carries out sintering after the front surface of the N-type nano black silicon prepared forms N+ layer, silicon nitride layer and electrode layer successively namely obtaining N-type nano black silicon solar cell.
10. the preparation method of solar cell as claimed in claim 9, is characterized in that, described electrode layer adopts full aluminium to carry on the back print process and prepares.
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